Substituted bis(bromoacetoxy)-xylenes

ABSTRACT

Compounds having the formula   IN WHICH R is hydrogen or cyano and R1 is hydrogen or methyl, Y IS H, lower alkyl or halo, n is a whole integer of from 1 to 4, and the use of these compounds as biocides such as in controlling fungi and bacteria.

United States Patent Baker 1451 Aug. 1, 1972 [5 S UBSTETUTEDBIS(BROMOACETOXY)-- XYLENES [72] Inventor: Don R. Baker, Orinda, Calif.

[73] Assignee: Staufler Chemical Company, New

York, NY.

[22] Filed: Aug. 28, 1969 [21] App1.No.: 853,973

FOREIGN PATENTS OR APPLICATIONS 566,283 11/1958 Canada ..260/487 PrimaryExaminer-Lorraine A. Weinberger Assistant Examiner-John F. TerapaneAttorney-Daniel C. Block, Edwin H. Baker and Albert J. Adamcik [57]ABSTRACT Compounds having the formula Yn v R O O R Br-(J-JJ OCH CHO 3Br1'1 1'11 R1 1'1 in which R is hydrogen or cyano and R is hydrogen ormethyl, Y [S H, lower alkyl or halo, n is a whole integer of from 1 to4, and the use of these compounds as biocides such as in controllingfungi and bacteria.

3 Claims, No Drawings 1 SUBSTITUTED BIS(BROMOACETOXY)-XYLENES SUMMARY OFTHE INVENTION This invention comprises novel compositions of matter andtheir use as biocides. More particularly, the invention relates tocompositions of matter having the formula wherein R is selected from thegroup consisting of hydrogen and cyano; R is selected from the groupconsisting of hydrogen and methyl; Y is selected from the groupconsisting of hydrogen, lower alkyl, and halo, n is a whole number from1 to 4, and the use of these compositions as fungicides andbactericides.

DESCRIPTION OF PREFERRED EMBODIMENT In its most preferred form, thisinvention relates to compositions of matter having the formula wherein Ris selected from the group consisting of hydrogen and cyano and R isselected from the group consisting of hydrogen and methyl, Y is selectedfrom the group consisting of hydrogen, methyl, ethyl, chloro and bromo,n is a whole number from 1 to 3, and the use of these compositions asfungicides and bactericides.

Representative compounds of this invention are as follows:

a,a'-bis(bromoacetoxy)-o-xylene a,a'-bis(bromoacetoxy)-m-xylenea,a-bis(bromoacetoxy)-p-xylene a,a-bis(bromoacetoxy)-2-chloro-p-xylenea,a'-bis(bromoacetoxy)-2,3,5-tribromo-p-xylene a,a-bis(brornocyanoacetoxy )-2-chloro-p-xylene a,a'-bis(bromoacetoxy(-2-methyl-p-xylene The compounds of the present inventionare particularly useful in inhibiting the growth of bacteria and fun-The compounds may be prepared by reacting a compound of the formula R OBr--ii-hal (reactant A) with a compound (reactant B) having the formulawherein R is selected from the group consisting of hydrogen and methyl,Y is selected from the group consisting of hydrogen, lower alkyl, andhalo, and n is a whole number from 1 to 4.

The concentrations employed are not particularly critical, althoughgenerally a slight excess of the acetyl halide (reactant A) will beemployed. A suitable concentration will thus be from about 2.0 mols toabout 2.7 mols of the acetyl halide (reactant A) per mole of diol(reactant B), although additional quantities of reactant A may bepresent. The preferred range of concentration will be from about 2.0mols to about 2.3 mols of (reactant A) per mole of (reactant B).

The reactions are preferably carried out under anhydrous conditions inthe presence of a base such as pyridine or triethylamine and in asolvent for the reactants. Suitable solvents include ether, benzene,chloroform or tetrahydrofuran. Reactions of this type are normallyexothermic so that the addition of heat is not required. In actuality,cooling may sometimes be required to control the reaction temperature.The reaction will normally be carried out at a temperature of from about0C. to about 50C.

While generally it is preferred that each R group be identical in thecompounds of the invention, it is not a requirement, and compoundswherein the reacted acyl moieties contain differing acyl moieties arecontemplated. Similarly, it is not necessary that each R group beidentical in the hydroxy containing aromatic precursor. These may besynthesized in the case of differing R groups by masking" one hydroxylgroup on the diol (reactant B) by procedures well known in the art, suchas with a tetrahydropyranyl ether, reacting the acyl halide with theremaining exposed hydroxyl group on (reactant B), then removing themasking influence such as by hydrolysis from the intermediate soprepared, and reacting the acyl halide with the resultant product toform the acetoxy compounds of the invention. The compounds of thisinvention can be recovered from the reaction mixture and purified bystandard procedures.

Preparation of the compounds of this invention is illustrated by thefollowing examples:

EXAMPLE 1 Preparation of a,a-bis(bromoacetoxyyp-xylene Approximately82.9 grams (0.6 mols) of 1,4- benzenedimethanol is suspended by faststirring in 700 ml. of chloroform. Simultaneously, 242.3 grams (1.2mols) of bromoacetyl bromide and 121.4 grams (1.2 mols) of triethylamineare added to the system. The reaction temperature is held between 10 and15C. The stirring is continued for about 1 hour and the system isallowed to come to room temperature.

The reaction mixtures are then washed several times with water, driedover MgSO. and stirred with activated charcoal for about one hour. Afterremoving the charcoal by filtration, the chloroform is evaporated,leaving 187.7 grams of liquid. n 1.5491. N.M.R. spectra confirmsstructure.

EXAMPLE II Preparation of a,a-bis(bromoacetoxy)-2-bromo-pxylene Theprocedure of Example I is repeated, using grams of2-bromo-l,4-benzenedimethanol instead of the 1,4-benzenedimethanol.

EXAMPLE n1 Preparation of a,a-bis(bromoacetoxy)-2-methyl-pxylene Theprocedure of Example I is repeated, utilizing 99 grams ofZ-methyl-1,4-benzenedimethanol instead of the 1,4-benzenedimethanol.

EXAMPLE lV Preparation of a,oz-bis(bromoacetoxy)-2-chloro-pxylene Theprocedure of Example I is repeated, utilizing 103 grams of Z-chloro-l,4-benzenedirnethanol instead of the 1,4-benzenedimethanol.

EXAMPLE V Preparation of a,a-bis(bromoacetoxy)-4-chloro-mxylene Theprocedure of Example I is repeated, utilizing 103 grams of4-chloro-l,3-benzenedimethanol instead of the 1,4-benzenedimethanol.

In order to demonstrate usefulness, the following tests were conductedusing a,a-bis( bromoacetoxy)-pxylene as exemplary of the compounds ofthe invention.

In Vitro Agar Test This test measures the bactericidal and fungicidalproperties of a compound when in contact with a growing bacterium orfungi in an artificial medium. The test is conducted by adding 20 ml.portions of a suitable warm sterile agar solution into 20 X 100 mm.petri dishes. Next, the test compound is added to the petri dishes atcertain concentrations expressed as pig/ml. and mixed with the warmmobile agar solution. This treated agar mixture is then allowed to coolto room temperature and solidify. Cells of the particular bac teria orfungi are then streaked on the surface of the solidified agar, and arethen incubated for such a length of time that untreated samplescontaining notoxicant show luxurious growth typical of the particularorganism. This time varies from 24 hours to 1 week depending upon theparticular organism. The fungi are incubated at 30C. and the bacteriaare incubated at 37C. Nutrient agar is used as the medium in this testfor the bacteria. Potato dextrose agar is the medium used in this testfor the fungi with the exception of Pullularia pullulans andTrichophyton mentagrophytes where Emmons agar is used. The table belowshows the results when a,a-bis-(bromoacetoxy)-p-xylene is used as thetoxicant in this test.

TABLE 1 Minimum inhibitory Concentration pg/ml.

Organism Bacteria;

Enterobacler aerogenes Bacillus ceres Brevibaclerium ammoniagenesStaphylococcus aureas Pullularia put'lulans Trichophymn memagrophylerindicates partial control at this concentration.

As can be seen by the test results, the compositions of the inventionmay be used in killing bacteria and fungi. The compositions may beapplied directly to the particular undesired biological organism or maybe applied to a locus to be protected. in either event, it is of coursenecessary that the unwanted organism receive an efiective dosage oramount, i.e., an amount sulfcient to kill or retard growth. Thecompositions may be applied to or in textiles, leather, paint, soaps,paper, wood, plastic, oil, and any other substances susceptible ofgrowth of undesirable biological organisms.

The compositions are normally employed with a suitable carrier and maybe applied as a dust, spray, drench or aerosol. The compositions thusmay be applied in combination with solvents, diluents, various surfaceactive agents (for example detergents, soaps or other emulsifying orwetting agents, surface active clays) carrier media, adhesives,spreading agents, humectants and the like. They may also be combinedwith other biologically active compositions, including other fungicidesand bactericides, insecticides, growth stimulators, acaricides,herbicides, molluscicides, algaecides, etc., as well as withfertilizers, soil modifiers, etc. The compositions of the invention maybe used in combination with an inert carrier and a surface active oremulsifying agent, and may also be applied in combination with otherbiologically active materials, in conjunction with a carrier and asurface active or emulsifying agent. The solid and liquid formulationscan be prepared by any of the conventional methods well-known by thoseskilled in the art. Since the amount of active agent required will varyaccording to the biological organism treated, precise limits on theamounts employed cannot be given. Determination of the optimum effectiveconcentration for a specific application is readily conducted by routineprocedures, as will be apparent to those skilled in the art. Asindicated, the amount applied in a given case will be an efiectiveamount, i.e., an amount suflicient to give the type of control desired.

Various changes and modifications may be made without departing from thespirit and the scope of the invention described herein, as will beapparent to those skilled in the art to which it pertains.

lclaim:

l. A compound having the formula wherein R is selected from the groupconsisting of hydrogen and methyl; Y is selected from the groupconsisting of hydrogen, lower alkyl, chloro, and bromo, and n is a wholenumber from 1 to 4.

2. The compound of claim 1 wherein Y is selected from the groupconsisting of hydrogen, methyl, ethyl,

chloro, and bromo, and n is a whole number from 1 to 3.

3. The compound of claim 2 wherein R is hydrogen and Y is hydrogen.

UNITED STAT LS PATENT OFFTLCE CERTIFIC TE GP CQRREQTIQN Patent No. 3,681,439 Dated August 1., 1972 Don R. Baker Inventor(s) It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

ATTACHb EN'I "A" In Examples I through V, in each instance, the portionofthe line reading "Preparation of t, k-bis(bromoacetoxy)", should. becorrected to read Preparation of d Q-bis (bromoacetoxy) In Column 4,Claim 1-, the formula should be corrected to read:

--- Br-c-cocl i HOC-(E-Br H R R H UNITED STA'iES PA'IENT OFFICECERHIICA'IL OF (JORRELCTION Patent No. 3.681.439 Dated August 1, 1972 lt D01! R0 i It is certified that error appears in the aboveand that saidLetters Patent are hereby corrected as identified patent shown below:

ATTACHMENT "B" The title should be corrected to read:

--- SUBSTITUTED g, 0-BIS(BROMOACETOXY)-XYLENES Signed and sealed this6th day of March 1973.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Commissioner of PatentsAttesting Officer

2. The compound of claim 1 wherein Y is selected from the groupconsisting of hydrogen, methyl, ethyl, chloro, and bromo, and n is awhole number from 1 to
 3. 3. The compound of claim 2 wherein R ishydrogen and Y is Hydrogen.